Synthesis and Excimer Formation Properties of Electroactive Polyamides Incorporated with 4,5-Diphenoxypyrene Units

A new dietherpyrene-cored diamine monomer, namely, 4,5-bis(4-aminophenoxy)pyrene, was successful synthesized and formed a series of electroactive polyamides with an aryloxy linkage in a polymer main chain and bearing pyrene chromophore as a pendent group using conventional one-pot polycondensation reactions with commercial aromatic/aliphatic dicarboxylic acids. The resulting polyamides exhibited good solubility in polar organic solvents and, further, can be made into transparent films. They had appropriate levels of thermal stability with moderately high glass-transition values. The dilute NMP solutions of these polyamides exhibited pyrene characteristic fluorescence and also showed a remarkable additional excimer emission peak centered at 475 nm. Electrochemical studies of these polymer films showed that these polyamides have both p- and n-dopable states as a result of the formation of radical cations and anions of the electroactive pyrene moieties.

New transparent and thermally stable cardo poly(ether imide)s derived from 10,10-bis[4-(4-amino-2-pyridinoxy)phenyl]-9(10H)-anthrone

A new diamine bearing flexible ether, rigid pyridine, and bulky anthrone pendent group, 10,10-bis[4-(4-amino-2-pyridinoxy)phenyl]-9(10 H)-anthrone (BAPPA), was prepared in three steps from anthrone. BAPPA was reacted with six conventional aromatic dianhydrides in N, N-dimethylacetamide (DMAc) to form the corresponding new poly(ether imide)s (PEIs) via the poly(ether amic acid) (PEAA) precursors with inherent viscosities ranging from 0.85 dL g−1 to 1.26 dL g−1 and thermal imidization. All the PEAAs could be cast from DMAc solution and thermally converted into transparent, flexible, and tough PEI films with tensile strength of 72.2–112.4 MPa, tensile modulus of 1.8–2.1 GPa, and elongation at break of 10–18%. These PEIs were predominantly amorphous and displayed excellent thermal stability with the glass transition temperature of 290–388°C, the 5% weight loss temperature of 480–514°C, and the residue of 68–43% at 800°C in nitrogen. The PEIs derived from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 4,4′-hexafluoroisopropylidenediphathalic anhydride exhibited excellent solubility in organic solvents such as N-methyl-2-pyrrolidinone, DMAc, N, N-dimethylformamide, pyridine, and even in tetrahydrofuran. Meanwhile, these PEIs also exhibited high optical transparency with the ultraviolet cutoff wavelength in the 374–427 nm range and the wavelength of 80% transparency in the range of 468–493 nm.

Synthesis of aromatic, soluble, and thermally stable polyamides derived from new diamine containing unsymmetrical phenolphthalein and imidazole pendent group

A novel diamine monomer containing unsymmetrical phenolphthalein and triaryl imidazole pendant group, 3,3-bis(4-(4-amino-2-(4,5-diphenyl-1H-imidazol-2-yl)phenoxy)phenyl)isobenzofuran-1(3H)-one (BADPPI), was successfully prepared in three steps. The novel diamine monomer BADPPI was directly polymerized with commercially available diacids, such as terephthalic acid, isophthalic acid, pyridine-2,6-dicarboxylic acid, and adipic acid, to obtain corresponding polyamides (PAs). The resulting novel aromatic PAs were obtained in high yields and moderate inherent viscosities in the range of 0.52–0.57 dL g−1 and exhibited excellent solubility in aprotic polar solvents, such as N,N-dimethylacetamide , N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, meta cresol, and pyridine. PAs showed high glass-transition temperatures between 191°C and 277°C. Thermogravimetric analysis of the PAs indicated a 10% weight loss ( T10%) in the temperature range of 382–473°C and char yields at 600°C under nitrogen atmosphere in the range of 56–70% depending on the diacids monomer used for the PAs preparation.

Modeling of Azobenzene-Based Compounds

Azobenzene is by far the most studied photochromic molecule and its applications range from optical storage to bio-engineering. To exploit the great potential of azobenzene, one must achieve deep understanding of its photochemistry as single molecule in solution AS WELL AS in-chain moiety and pendent group in macromolecular structures. With the advent of computer-aided simulation scientists have been able to match experimental data with computational models. In this chapter, a review on the modeling of azobenzene-containing molecules in different conditions and environments IS provided with a special focus on advanced applications of photo-controllable materials, such as molecular machines and photoactivation of bio-molecules.

Novel polyimides based on diamine containing thiazole units with thioether linkage and pyridine as pendent group

Three new organic-soluble polyimides (PIs) bearing flexible thioether linkages, thiazole, and pyridine ring units were synthesized from a novel thioether-bridged diamine monomer and commercially available aromatic dianhydrides (1–3) via chemical imidization method. The resulting polymers were obtained in high yields and possessed inherent viscosities in the range of 0.67–0.89. The PIs are characterized by Fourier-transform infrared (FTIR), nuclear magnetic resonance (NMR), differential scanning calorimetry, and thermogravimetric analysis (TGA). All of the PIs exhibited excellent solubility in polar solvent. The polymers showed good thermal stability with glass transition temperatures ( Tgs) in the range of 194–244°C, and decomposition temperatures ( T5%) exceeding 300°C were observed using TGA in nitrogen atmosphere for the current polymers.

Structural, thermal and mechanical properties of polymer nanocomposites based on organosoluble polyimide with naphthyl pendent group and layered double hydroxide

In this study, a soluble aromatic polyimide (PI) with naphthyl pendent group was initially synthesized by the reaction of pyromellitic dianhydride (PMDA) with 5-methyl- N,N-bis(4-nitrophenyl)naphthalen-1-amine. Then, via co-precipitation reaction of zinc nitrate hexahydrate and chromium nitrate nonahydrate, Zn/Cr-layered double hydroxide (LDH) was synthesized using hydrothermal techniques. Finally, different novel nanocomposites (NCs) based on PI and Zn/Cr-LDH (1, 2, 4 wt%) were produced through in situ polymerization. The resulting materials were characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetry analysis (TGA), field emission scanning electron microscopy, transmission electron microscopy, and mechanical testing. According to the TGA results, the prepared NCs showed high thermal stability at higher temperature due to the good dispersion and homogeneity of Zn/Cr-LDH in polymeric matrix. Consequently, the mechanical properties of the synthesized NCs were enhanced by the incorporation of 2 wt% Zn/Cr-LDH in the polymer matrix.

Interpenetrating polymer networks formed by cyanate esters and phenylethynyl-terminated imides

An oligomeric phenylethynyl-terminated imide (PETI) has been formulated with a cyanate ester (CE) with and without the addition of a compatibilizer 2,2′-diallylbisphenol A (DABPA) forming interpenetrating polymer networks (IPNs). Modulated differential scanning calorimetry (mDSC) was used to monitor the curing of the resin mixtures. The formation of various resulting IPNs was verified using mDSC, dynamical mechanical thermoanalysis (DMTA), thermal gravimetry analysis and scanning electron microscopy. Furthermore, it could be shown by mDSC and DMTA that a covalent bond of the separated CE and PETI networks could be achieved by the addition of DABPA. In this regard, a reaction mechanism is proposed for the cross-linking reaction between the allylic pendent group of DABPA and the phenylethynyl end-group of the PETI resin. The cured resin specimens showed to have very high heat resistance and very high glass transition temperatures up to 330°C.